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Halothane-Diethyyl Ether Ratios During Halothane-Diethyl Ether Azeotrope Anaesthesia

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Halothane-Diethyyl Ether Ratios During Halothane-Diethyl Ether Azeotrope Anaesthesia HALOTHANE-DIETHYYL ETHER RATIOS DURING HALOTHANE-DIETHYL ETHER AZEOTROPE ANAESTHESIA F. W. Cr~RVENKO,M.D., AND S. L. VANDEWATER, M.D. Q H~tLOTI-n~NE AND DmTHYL ETHER form an azeotrope which has been in use as an inhalation anaesthetic since it was reported in 1958.1 An azeotrope may be simply defined as a constant-boillng-point mixture. Azeotropes are stable to fractional distillation but can be separated by extractive distillation~ and gas chromatogra- phy. The type of bonding of halothane and diethyl ether is probably of low energy and is either by dipole moments or hydrogen bonds. 2 The stability of the azeotrope in the body has been questioned, since studies using infrared spec- trometry showed changing halothane-diethyl ether ratios in breath during anaesthesia with the azeotrope, suggesting that biological mechanisms may be in- volved in the breakdown of the azeotrope, a Changing halothane-diethyl ether ratios may imply changing flammability conditions ff "free" diethyl ether is present. Using three volumes per cent inspired concentration, blood concentrations of each component of the azeotrope have been predicted, 1 and based on the pre- dicted blood levels of diethyl ether, it has been suggested that anaesthesia with the azeotrope offers an advantage over anaesthesia with halothane alone. The present study is concerned with the determination of halothane--diethyl ether ratios during laboratory and clinical situations and the measurement of blood halothane and diethyl ether concentrations during azeotrope anaesthesia using gas chromatography. METI-IOn Calibration studies The chromatographic conditions consisted of an F & ~ model 700 chromato- graph with a flame ionization detector, a 6 foot )< 1/8 inch O.D. copper column packed with Porapak Q 50/80 mesh, and a 1 millivolt Moseley recorder. The injection port temperature was 170 ~ C, oven temperature 130 ~ C, detector tem- perature 200 ~ C, and helium carrier gas flow rate was 50 ml per minute. Quan- titation of the area under the halothane and diethyl ether peaks was done by a disc integrator. Sample injections of 400 microlitres of azeotrope vapour were used. All samples were done in duplicate except in the clinical study on respired gas. The azeotrope was made using 66 parts halothane and 34 parts diethyl ether vol/vol. 4 Repeatability studies were done on azeotrope vapour emerging *Department of Anaesthesiology,Queen's Universityat Kingston. ~Extractive distillation is defined as distillation in-the presence of a solvent which is rela- tively non-volatile compared to the components to be separated, and which is selected to enhance the relative volatility of the components. 70 Canad. Anaesth. Soe. J., vol. 17, no. 1, January 1970 CERVENKO & VANDEWATER: HALOTHANE-DIETHYL ETHER RATIOS 71 from a Fluotec vaporizer with a carrier gas flow of three litres of oxygen and three litres of nitrous oxide per minute. The halothane-diethyl ether ratios were deter- mined in five lots of azeotrope made on five different days and over a storage period of 9.5 days at room temperature. Laboratory studies Circle absorber study. To determine the effect of soda lime, carbon dioxide, and water vapour on azeotrope, the following study was done in quadruplicate. Azeotrope vapour from a Fluotec vaporizer was introduced into a closed circle with the absorber off, using equal parts oxygen and nitrous oxide and an addi- tional reservoir bag at the face piece end until both reservoir bags were nearly full. The gas was circulated by alternate squeezing of the reservoir bags. After ten minutes, 400 mierolitres of gas from the inspiratory side were sampled and injected into the chromatograph. A Boyle Mark IH absorber canister containing fresh soda lime was added to the circuit, and the gas was circulated for ten minutes and again sampled. One hundred per cent carbon dioxide was intro- duced into the circle continuously for three to five minutes and circulated until the absorber became warm. The system was again sampled. The experiment was repeated with 250 ml of water added to the soda lime canister, and the carbon dioxide, soda lime, and water vapour from the canister introduced simultaneously. In vitro blood and water study. Samples of 10 ml heparinized whole blood were added to 38.5 ml capacity vials sealed with a rubber stopper and weighed. Azeotrope was injected through the stopper and the vial reweighed and mixed. After equilibration in a water bath at 20 ~ C, 25 ~ C, and 37 ~ C • 1.5 ~ C the halothane-diethyl ether ratio was determined by sampling 400 microlitres of the gas phase and injecting them into the chromatograph. This was repeated using 10 ml samples of water equilibrated at 21 ~ C, 25 ~ C, and 37 ~ C. Clinical study. Six premedicated patients undergoing elective minor urologic or plastic surgical procedures were induced with intravenous thiopental or diaze- pare and given halothane--diethyl ether azeotrope from the same Fluotec vapori- zer. Three patients were anaesthetized using a Fluotee vaporizer outside a circle absorber system with the vaporizer set up to 2.5 during induction and 0.75 to 1.5 for maintenance and with carrier gases of 3 litres of oxygen and 3 litres of nitrous oxide per minute. Respirations were spontaneous. Gas samples were taken at intervals for chromatographic analysis from the inspiratory and expiratory sides of the corrugated tubing. After inhalation anaesthesia had been established for 13 to 15 minutes, simultaneously 10 ml heparinized radial artery and peri- pheral venous blood samples were taken anaerobically for detelznination of halo- thane and diethyl ether concentrations. Arterial and venous blood samples were taken from an additional patient anaesthetized with azeotrope for 38 minutes. End expiratory gas samples were taken three to five minutes following cessation of anaesthesia. Three patients were anaesthetized with azeotrope using a non-rebreathing circuit with a flow of 4 litres of oxygen and 4 litres of nitrous oxide per minute. End expiratory breath samples were taken at intervals during anaesthesia, with 72 CANADIAN ANAESTHETISTS'SOCIETY JOURNAL spontaneous respiration and following cessation of anaesthesia for chromato- graphic analysis. In three patients end expired halothane and diethyl ether were quantitated during recovery from azeotrope anaesthesia. It was assumed that at a Fluotec setting of 1.0 and 8 litres of gas passing through the vaporizer, two-thirds volume per cent halothane and one-third volume per cent diethyl ether emerged. 4 The integrated areas of the halothane and diethyl ether chromatographic peaks from this Fluotec setting were used to determine the expired breath concentrations. Blood halothane and diethyl ether concentrations were determined by blood- air equilibration. 5 A calibration curve for halothane and diethyl ether was made by placing 10 ml samples of heparinized whole blood into three 36.5 rnl rubber stoppered vials, weighing, injecting three different halothane and diethyl ether eoneentrations, and reweighing. The vials were mixed and equilibrated in a water bath at 22 ~ C for thirty minutes. Four hundred microlitre samples of the gas phase in the vials were injected into the chromatograph and the calibration curve constructed. Blood samples from the anaesthetized patients were similarly equilibrated at 22 ~ C, and the blood concentration determined from the calibration curve. OBSERVATIONS AND DISCUSSION Calibration Figure i is a sample ehromatogram of halothane--diethyl ether azeotrope. Elution times were eighteen seconds for water vapour, 100 seconds for diethyl ether, and 155 seconds for halothane. The mean halothane-diethyl ether vapour ratio of five lots of azeotrope was found to be 1.65 ___ 0.03 (st.) and the ratio was unaltered throughout all Fluotec settings of 0.5 to 4.0. The halothane--diethyl ether ratio of azeotrope changed little when determined on ten different days over a period of twenty-five days with a mean ratio of 1.60 ___ 0.01 (sE). Injec- tion repeatability of ten consecutive gas samples of azeotrope at a 1 per cent Fluotec setting with 3 litres of oxygen and 3 litres of nitrous oxide per minute resulted in a mean integrated area of 1,610 ___ 11 (SE) for diethyl ether and 2,753 • 38 (SE) for halothane. Laboratory studies Figure 2 shows the results of the circle absorber experiment. The mean halo- thane-diethyl ether ratios following contact with soda lime, soda lime and carbon dioxide, and soda lime, carbon dioxide, and water vapour are statistically sig- nificantly different (p < 0.01) from that of azeotrope. The mean ratios after contact with carbon dioxide and carbon dioxide with water vapottr were not statistically different from the ratio after contact with soda lime alone (p > 0.05). Thus, soda lime can break down the azeotrope. Since the ratio increased, halothane is present in a proportionately greater quantity in the gas phase. Soda lime is known to adsorb inhalation anaesthetics, and the results suggest that diethyl ether is adsorbed onto soda lime in proportionately greater quantity than halothane. CERVENKO & VANDEWATER: HALOTHANE-DIETHYLETHER RATIOS 73 FmtraE 1. Chrornatogram of diethyl ether (1) and halothane (2). In vitro blood and water study. Table I lists the altered halothane--diethyl ether ratio of azeotrope after the addition of different concentrations to blood and water, and the effect of temperature on the ratio. Since the ratio increased, proportionately more halothane is present in the gas phase. The change in ratio with temperature and concentration of azeotrope in both blood and water is com- patible with the fact that halothane and diethyl ether have different slopes of their blood/gas and water/gas partition coefficients at different temperatures. There is a marked difference in halothane--diethyl ether ratios in blood compared to water, with more halothane being present in the gas phase above water. This is explain- able by the fact that the blood/gas partition coefficient for halothane at 37 ~ C is 2.3 and the water/gas coefficient 0.74, signifying that halothane is more soluble in blood than in water.
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